CN103545525A - Lithium ion battery nano composite positive-negative electrode material containing three-dimensional conductive network as well as preparation method thereof - Google Patents
Lithium ion battery nano composite positive-negative electrode material containing three-dimensional conductive network as well as preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium ion battery nano composite positive-negative electrode material containing a three-dimensional conductive network as well as a preparation method thereof. Technical key point is that the three-dimensional conductive network is built by comprehensively using a modified and dispersed one-dimensional conductive nano material with great slenderness ratio and high strength and a zero-dimensional nano conductive material under action of a binding agent, so that mechanical strength and processing performance of the positive-negative electrode material of the lithium ion battery as well as transmissibility of electrons among particles are improved, and therefore, a problem that the typical lithium ion battery electrode material is poor in great multiplying power performance and short in cycle life is solved. The preparation method of the lithium ion battery nano composite positive-negative electrode material comprises the following steps: firstly, adding the one-dimensional conductive nano material into water or an organic solvent containing a surfactant for ultrasonic treatment and stirring treatment so as to sufficiently disperse one-dimensional conductive nano material; and then, respectively adding the dispersing liquid into a zero-dimensional conductive agent, a binding agent and the positive-negative electrode material for ultrasonically stirring and stirring for a certain time at a high speed to obtain the lithium ion battery nano composite positive-negative electrode material containing the three-dimensional conductive network.
Description
Technical field
The present invention relates to lithium ion battery electrode material technical field, relate in particular to contain three dimensions conductive network there is high power capacity, long-life, the compound positive and negative electrode material of powerful lithium ion cell nano and preparation method.
Background technology
The whole world is faced with increasing carbon emission reduction pressure, and according to the statistics of world car tissue (OICA), motor vehicle exhaust emission amount has occupied CO
2approximately 16% of total emission volumn.Therefore, promoting the use of clean energy vehicle, is an imperative major action.Development of EV with electrokinetic cell to reducing the degree of dependence of oil, reducing CO
2discharge capacity, alleviate Global Greenhouse Effect and be significant.
Battery is bottleneck maximum on current new-energy automobile technology and cost, and traditional lead-acid battery, nickel-cadmium cell, Ni-MH battery etc., because energy density is lower, pollute the problems such as bad border and can not meet well the demand in market.At present having most the battery of development potentiality is lithium ion battery, lithium ion battery has that energy density is large, working voltage platform is high, has extended cycle life, self discharge is little, memory-less effect, environmental friendliness, thermal stability and the outstanding advantages such as security performance is good, there is combination property best in current battery, meet social development needs, its range of application is more and more extensive.But the large high rate performance of lithium ion battery and cycle life are still difficult to meet the requirement of electric automobile now.
In practical application, conventionally need to be coated carbon black or the graphite granule conductive agent of 2-15wt.%, form effective conductive network, to improve conductivity.In theory, by particle surface, being coated raising conductive capability is based on " exceed and ooze " principle: in the basis material of insulation, add after electric conducting material, when the electric conducting material content adding surpasses after a certain " percolation threshold ", between conductive additive, formed conductive network, conductivity increases substantially suddenly.But repeatedly, after charge and discharge cycles, the conductive network being barricaded as with carbon black or graphite granule can rupture, conductivity and specific capacity all will sharply decline, and cause its cycle life sharply to shorten.And the addition of carbon black or graphite granule conductive agent is relatively many, reduced the specific capacity of electrode material.Therefore, be necessary to find more effective conductive additive.
According to grid, exceed and ooze theoretical model theoretical explanation: only have after contiguous lattice point is all occupied by conductive agent particle, these lattice points could form a conductive network.Suppose that the probability that in grid, each lattice point is occupied by conducting particles is P, all the other probabilities that are not occupied are 1-P.The probability that forms conductive network is directly proportional to P, and the increase of P can realize by the quantity of increase conductive agent particle or the shape of change conductive agent.When P increases to a certain critical value Pc(percolation threshold) time, will there is percolation transition, system resistivity can reduce suddenly.Theory can be inferred thus: while using 1-dimention nano electric conducting material as conductive agent, because 1-dimention nano electric conducting material draw ratio is larger, in lattice theory model, a 1-dimention nano electric conducting material just can occupy a plurality of adjacent lattice points simultaneously, and zero-dimension nano conducting particles once can only occupy a lattice point, and could form conductive network after only having adjacent lattice point to be occupied, thereby the critical value Pc of 1-dimention nano electric conducting material is little more a lot of than zero-dimension nano conducting particles, therefore the probability that the 1-dimention nano electric conducting material that under equal conditions, draw ratio is large forms conductive network is high more a lot of than spherical zero-dimension nano conducting particles.Based on this, 1-dimention nano electric conducting material can replace traditional carbon black or graphite, as good conductive additive.
But, the high surface energy that the winding causing due to one-dimensional electric nano material big L/D ratio and bigger serface cause, particle exists stronger Van der Waals force to interact, generally highly to assemble or mutually to twine assorted state, exist, and height accumulation shape tends to weaken the characteristics such as excellent electricity that single one-dimensional electric nano material has, mechanics, and the contact probability of monodimension nanometer material and positive electrode is declined greatly, thereby reduced the utilance of material and the consistency of the internal resistance of cell.Simultaneously, 1-dimention nano electric conducting material is owing to generally having high strength and stiffness, be difficult to bend to and the shape and the diameter that are the spherical or approximate spherical suitable yardstick of lithium ion battery positive and negative electrode material granule, thereby, while using 1-dimention nano electric conducting material separately, one-dimensional electric material is difficult to cover all, equably all surface of lithium ion battery positive and negative electrode material granule, forms efficient conductive network; And, the large technical bottleneck problem of capacity attenuation when existing experimental result does not still solve heavy-current discharge.
Summary of the invention
The object of the invention is in order to solve large high rate performance and the poor problem of cycle life of typical power battery electrode material, provide a kind of contain three dimensions conductive network there is high-performance, the compound positive and negative electrode material of high-power, long-life lithium ion cell nano and preparation method.
Technical essential of the present invention: preparation is harmless, homodisperse big L/D ratio, high strength monodimension nanometer material, under the effect of binding agent, build three dimensions conductive network with zero-dimension nano conductive particle, the conducting power of electronics between mechanical strength, processing characteristics and the particle of raising lithium ion battery positive and negative electrode material.
The invention provides the compound positive and negative electrode material of the lithium ion cell nano that contains three dimensions conductive network, comprise positive and negative electrode active material, conductive agent, binding agent, wherein, positive active material is LiFePO4, lithium manganese phosphate, cobalt phosphate lithium, LiNiPO, cobalt acid lithium, LiMn2O4, lithium nickelate, ternary compound oxides nickle cobalt lithium manganate; Negative electrode active material is native graphite, MCMB, amorphous carbon, hard charcoal, pyrolytic carbon, petroleum coke, pitch based carbon fiber carbonaceous material, lithium titanate, silica-based, tin-based material; Conductive agent is one or more in one dimension and zero-dimension nano electric conducting material; Described binding agent is one or more in Kynoar, polytetrafluoroethylene, polyvinyl alcohol, acid polyethylene butyral, polyacrylic acid formicester, carboxymethyl cellulose, butadiene-styrene rubber, methylcellulose, hydroxypropyl methylcellulose, ethyl cellulose.
Three dimensions conductive network described in the present invention is built with zero-dimension nano electric conducting material after disperse modified by one-dimensional electric nano material.
One or more in the nanotube that one-dimensional electric nano material described in the present invention is conduction, nano wire, nanobelt, nanometer rods.
One-dimensional electric nano material diameter described in the present invention is nanometer scale, and L/D ratio example is greater than 1, has high strength, high conductivity.
Zero-dimension nano electric conducting material of the present invention is one or more nano-powder in carbon black, acetylene black, superconduction carbon black, graphite, copper powder, silver powder, zinc powder, aluminium powder.
Surfactant described in the present invention is polyvinylpyrrolidone, alkylphenol-polyethenoxy (10) ether, polyacrylamide, polyacrylate, polyurethane, polyisobutene succinimide, poly(ethylene oxide) ether, hydroxyethylcellulose, sodium hydroxyethyl cellulose, lauryl sodium sulfate, dodecyl poly(ethylene oxide) ester, fatty acid polyglycol oxirane ester, alkoxyl polyalkylene oxide acrylate, polycaprolactone, polystyrene-vinyl pyrrolidone, polystyrene, N, one or more in N-divinyl acrylamide.
The preparation method of the compound positive and negative electrode material of the lithium ion cell nano that contains three dimensions conductive network of the present invention, comprises the following steps:
(1) surfactant is joined in water or organic solvent and fully dissolved according to the concentration of (0.05-10) %, again by one-dimensional electric nano material according to surfactant mass ratio be (0.1-10): 1 joins in above-mentioned solution, respectively ultrasonic and stir process (1-10) hour with (1-24) hour.
(2) by zero dimension electrical-conductive nanometer material, binding agent and positive and negative electrode active material according to one-dimensional electric nano material mass ratio be (1-20): (1-10): (75-95): (0.1-10) join successively in above-mentioned dispersion liquid, ultrasonic (0.1-10) hour, stirs (0.1-10) hour afterwards.
Organic solvent described in the present invention is ethanol, dimethyl formamide, N, 1-METHYLPYRROLIDONE, chloroform, butanols, cyclohexanol, first phthalein amine, dimethyl sulfoxide (DMSO), formic acid, glycerol, isopropyl alcohol, methyl alcohol, carrene, cyclohexanone.
Ultrasonic processing described in the present invention refers to ultrasonic oscillation processing, and stir process refers to mechanical agitation processing.
beneficial effect of the present invention
Before batch mixing first by the one-dimensional electric nano material of big L/D ratio, high strength, high conductivity ultrasonic and stir process under the effect of surfactant, make the coated layer of surface activating agent in its surface, destroy gathering and the winding of monodimension nanometer material itself, thereby realize dispersed in liquid phase of monodimension nanometer material.The effect of zero dimension electrical-conductive nanometer material is to be finely coated on active material surface, and one-dimensional electric nano material can well be together in series through the coated active material surface of zero dimension electrical-conductive nanometer material above-mentioned, under the effect of binding agent, form firmly three dimensions conductive network (Fig. 1), significantly improve the conducting power of electronics between mechanical strength, processing characteristics and the particle of lithium ion battery positive and negative electrode material, thereby solved large high rate performance and the poor problem of cycle life of typical lithium ion battery electrode material.
LiFePO4/1-dimention nano combination electrode material after modification of the present invention has following outstanding characteristic (Fig. 2) under large electric current (10C) discharging condition:
1. each charge and discharge cycles capacity attenuation 0.0075mAh/g;
2. cycle life is approximately 3400 times;
3. initial discharge capacity 125mAh/g;
4. coulombic efficiency is greater than 99.1%.
Lithium titanate/1-dimention nano combination electrode material after modification of the present invention has following outstanding characteristic (Fig. 3) under large electric current (10C) discharging condition:
1. each charge and discharge cycles capacity attenuation 0.0067mAh/g;
2. cycle life is approximately 3500 times;
3. initial discharge capacity 118mAh/g;
4. coulombic efficiency is greater than 99.5%.
Accompanying drawing explanation
Fig. 1 be the lithium-ion battery composite-electrode material with three dimensions conductive network being formed by zero dimension and 1-dimention nano electric conducting material prepared of the present invention schematic diagram (wherein, large empty circles represents electrode material, little black circle represents zero dimension electrical-conductive nanometer material, and straight line represents one-dimensional electric nano material).
Fig. 2 be LiFePO4/1-dimention nano combination electrode material after modification of the present invention and the electrode material before modification Performance Ratio.
Fig. 3 be lithium titanate/1-dimention nano combination electrode material after modification of the present invention and the electrode material before modification Performance Ratio.
Embodiment
Embodiment 1:
Under room temperature, 0.1 gram of surfactant is joined in 100 ml waters and fully dissolve, 0.1 gram of nano silver wire is joined in this solution, ultrasonic (1-10) hour, stirs (1-24) hour, obtains even, stable nano silver wire dispersion liquid; Add successively again zero dimension electrical-conductive nanometer material (0.1-2) gram, water-soluble binder (0.1-1) gram, LiFePO4/lithium titanate (7.5-9.5) gram, ultrasonic (0.1-10) hour respectively, stir (0.1-10) hour, obtain having the lithium ion cell nano composite material of three dimensions conductive network.
Embodiment 2:
Under room temperature, 0.1 gram of surfactant is joined in 100 ml waters and fully dissolve, 0.1 gram of silver nanoparticle rod is joined in this solution, ultrasonic (1-10) hour, stirs (1-24) hour, obtains even, stable silver nanoparticle rod dispersion liquid; Add successively again zero dimension electrical-conductive nanometer material (0.1-2) gram, water-soluble binder (0.1-1) gram, LiFePO4/lithium titanate (7.5-9.5) gram, ultrasonic (0.1-10) hour respectively, stir (0.1-10) hour, obtain having the lithium ion cell nano composite material of three dimensions conductive network.
Embodiment 3:
Under room temperature, 0.1 gram of surfactant is joined in 100 ml waters and fully dissolve, 0.1 gram of copper nano-wire is joined in this solution, ultrasonic (1-10) hour, stirs (1-24) hour, obtains even, stable copper nano-wire dispersion liquid; Add successively again zero dimension electrical-conductive nanometer material (0.1-2) gram, water-soluble binder (0.1-1) gram, LiFePO4/lithium titanate (7.5-9.5) gram, ultrasonic (0.1-10) hour respectively, stir (0.1-10) hour, obtain having the lithium ion cell nano composite material of three dimensions conductive network.
Embodiment 4:
Under room temperature, 0.1 gram of surfactant is joined in 100 ml waters and fully dissolve, 0.1 gram of copper nanotube is joined in this solution, ultrasonic (1-10) hour, stirs (1-24) hour, obtains even, stable copper nanotube dispersion liquid; Add successively again zero dimension electrical-conductive nanometer material (0.1-2) gram, water-soluble binder (0.1-1) gram, LiFePO4/lithium titanate (7.5-9.5) gram, ultrasonic (0.1-10) hour respectively, stir (0.1-10) hour, obtain having the lithium ion cell nano composite material of three dimensions conductive network.
Embodiment 5:
Under room temperature, 0.1 gram of surfactant is joined in 100 ml waters and fully dissolve, 0.1 gram of carbon nano-tube is joined in this solution, ultrasonic (1-10) hour, stirs (1-24) hour, obtains even, stable carbon nano tube dispersion liquid; Add successively again zero dimension electrical-conductive nanometer material (0.1-2) gram, water-soluble binder (0.1-1) gram, LiFePO4/lithium titanate (7.5-9.5) gram, ultrasonic (0.1-10) hour respectively, stir (0.1-10) hour, obtain having the lithium ion cell nano composite material of three dimensions conductive network.
Embodiment 6:
Under room temperature, 0.1 gram of surfactant is joined in 100 ml waters and fully dissolve, 0.1 gram of carbon nano-fiber is joined in this solution, ultrasonic (1-10) hour, stirs (1-24) hour, obtains even, stable carbon nano-fiber dispersion liquid; Add successively again zero dimension electrical-conductive nanometer material (0.1-2) gram, water-soluble binder (0.1-1) gram, LiFePO4/lithium titanate (7.5-9.5) gram, ultrasonic (0.1-10) hour respectively, stir (0.1-10) hour, obtain having the lithium ion cell nano composite material of three dimensions conductive network.
Embodiment 7:
Under room temperature, 0.1 gram of surfactant is joined in 100 ml waters and fully dissolve, 0.1 gram of silicon nanowires is joined in this solution, ultrasonic (1-10) hour, stirs (1-24) hour, obtains even, stable silicon nanowires dispersion liquid; Add successively again zero dimension electrical-conductive nanometer material (0.1-2) gram, water-soluble binder (0.1-1) gram, LiFePO4/lithium titanate (7.5-9.5) gram, ultrasonic (0.1-10) hour respectively, stir (0.1-10) hour, obtain having the lithium ion cell nano composite material of three dimensions conductive network.
Embodiment 8:
Under room temperature, 0.1 gram of surfactant is joined in 100 ml waters and fully dissolve, 0.1 gram of nano-tube is joined in this solution, ultrasonic (1-10) hour, stirs (1-24) hour, obtains even, stable nano-tube dispersion liquid; Add successively again zero dimension electrical-conductive nanometer material (0.1-2) gram, water-soluble binder (0.1-1) gram, LiFePO4/lithium titanate (7.5-9.5) gram, ultrasonic (0.1-10) hour respectively, stir (0.1-10) hour, obtain having the lithium ion cell nano composite material of three dimensions conductive network.
The description of above-mentioned several embodiment is mainly in order clearly to understand, to the invention is not restricted to cited embodiment here, and those skilled in the art are according to announcement of the present invention, and the improvement of making for the present invention and modification all should be within protection scope of the present invention.
Claims (9)
1. the compound positive and negative electrode material of lithium ion cell nano that contains three dimensions conductive network, described positive and negative electrode material comprises positive and negative electrode active material, conductive agent, surfactant, binding agent, it is characterized in that containing in positive and negative electrode material the three dimensions conductive network that one-dimensional electric nano material is built with zero dimension electrical-conductive nanometer material after disperse modified.
2. the compound positive and negative electrode material of the lithium ion cell nano that contains three dimensions conductive network according to claim 1, is characterized in that positive active material is LiFePO4, lithium manganese phosphate, cobalt phosphate lithium, LiNiPO, cobalt acid lithium, LiMn2O4, lithium nickelate, ternary compound oxides nickle cobalt lithium manganate; Negative electrode active material is native graphite, MCMB, amorphous carbon, hard charcoal, pyrolytic carbon, petroleum coke, pitch based carbon fiber carbonaceous material, lithium titanate, silica-based, tin-based material; Conductive agent is one or more in one dimension and zero dimension electrical-conductive nanometer material; Described binding agent is one or more in Kynoar, polytetrafluoroethylene, polyvinyl alcohol, acid polyethylene butyral, polyacrylic acid formicester, carboxymethyl cellulose, butadiene-styrene rubber, methylcellulose, hydroxypropyl methylcellulose, ethyl cellulose.
3. the compound positive and negative electrode material of the lithium ion cell nano that contains three dimensions conductive network according to claim 1, is characterized in that one or more in nanotube that described one-dimensional electric nano material is conduction, nano wire, nanobelt, nanometer rods.
4. the compound positive and negative electrode material of the lithium ion cell nano that contains three dimensions conductive network according to claim 1, it is characterized in that described one-dimensional electric nano material diameter is nanometer scale, L/D ratio example is greater than 1, has high strength, high conductivity.
5. the compound positive and negative electrode material of the lithium ion cell nano that contains three dimensions conductive network according to claim 1, is characterized in that described zero dimension electrical-conductive nanometer material is one or more in carbon black, acetylene black, superconduction carbon black, graphite, copper powder, silver powder, zinc powder, aluminium powder.
6. the lithium ion cell nano that contains three dimensions conductive network according to claim 1 is just compound, negative material, it is characterized in that described surfactant is polyvinylpyrrolidone, alkylphenol-polyethenoxy (10) ether, polyacrylamide, polyacrylate, polyurethane, polyisobutene succinimide, poly(ethylene oxide) ether, hydroxyethylcellulose, sodium hydroxyethyl cellulose, lauryl sodium sulfate, dodecyl poly(ethylene oxide) ester, fatty acid polyglycol oxirane ester, alkoxyl polyalkylene oxide acrylate, polycaprolactone, polystyrene-vinyl pyrrolidone, polystyrene, N, one or more in N-divinyl acrylamide.
7. the preparation method of the compound positive and negative electrode material of the lithium ion cell nano that contains three dimensions conductive network according to claim 1, is characterized in that following steps:
First surfactant is joined in water or organic solvent and fully dissolved according to the concentration of (0.05-10) %, again by one-dimensional electric nano material according to surfactant mass ratio (0.1-10): 1 joins in above-mentioned solution, respectively ultrasonic and stir process (1-10) hour with (1-24) hour;
By zero dimension conductive agent, binding agent and positive and negative electrode active material according to one-dimensional electric nano material mass ratio (1-20): (1-10): (75-95): (0.1-10) join successively in above-mentioned dispersion liquid, ultrasonic (0.1-10) hour, stirs (0.1-10) hour afterwards.
8. the preparation method of the compound positive and negative electrode material of the lithium ion cell nano that contains three dimensions conductive network according to claim 7, it is characterized in that described organic solvent is ethanol, dimethyl formamide, N, 1-METHYLPYRROLIDONE, chloroform, butanols, cyclohexanol, first phthalein amine, dimethyl sulfoxide (DMSO), formic acid, glycerol, isopropyl alcohol, methyl alcohol, carrene, cyclohexanone.
9. the preparation method of the compound positive and negative electrode material of the lithium ion cell nano that contains three dimensions conductive network according to claim 7, is characterized in that described ultrasonic processing refers to ultrasonic oscillation processing, and stir process refers to mechanical agitation processing.
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| CN105336942A (en) * | 2015-11-19 | 2016-02-17 | 上海空间电源研究所 | Fully-sealed Li-ion storage battery based on ternary cathode material and preparation method of fully-sealed Li-ion storage battery |
| CN105336922A (en) * | 2014-08-08 | 2016-02-17 | 苏州格瑞动力电源科技有限公司 | Preparation method and application for lithium ion battery negative electrode material based on photovoltaic silicon waste material |
| CN106463710A (en) * | 2014-04-25 | 2017-02-22 | 南达科他州评议委员会 | High capacity electrodes |
| CN107275598A (en) * | 2017-05-27 | 2017-10-20 | 广东烛光新能源科技有限公司 | A kind of lithium titanate anode material and preparation method thereof |
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| CN112490408A (en) * | 2020-12-03 | 2021-03-12 | 珠海冠宇电池股份有限公司 | Positive plate and lithium ion battery comprising same |
| CN112786846A (en) * | 2019-11-08 | 2021-05-11 | 恒大新能源技术(深圳)有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN113366667A (en) * | 2019-01-30 | 2021-09-07 | Sk新技术株式会社 | Secondary battery and method for manufacturing same |
| CN114883557A (en) * | 2022-03-07 | 2022-08-09 | 上海交通大学 | Preparation method of lithium iron phosphate composite positive electrode material with gold nanorods as conductive additive |
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| WO2024021086A1 (en) * | 2022-07-29 | 2024-02-01 | 宁德时代新能源科技股份有限公司 | Negative electrode slurry, preparation method therefor, negative electrode sheet, battery cell, battery, and electric device |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1207572A1 (en) * | 2000-11-15 | 2002-05-22 | Dr. Sugnaux Consulting | Mesoporous electrodes for electrochemical cells and their production method |
| CN101207193A (en) * | 2006-12-21 | 2008-06-25 | 比亚迪股份有限公司 | Method for preparation of electrode slurry |
| CN101335347A (en) * | 2008-08-01 | 2008-12-31 | 黄德欢 | Preparing method of highly conductive lithium iron phosphate anode material of lithium ionic cell |
| CN101567469A (en) * | 2008-07-08 | 2009-10-28 | 周雨方 | Power polymer lithium ion battery and fabricating process thereof |
| CN101651236A (en) * | 2009-08-31 | 2010-02-17 | 杭州万马高能量电池有限公司 | Fast chargeable lithium iron phosphate polymer lithium ion battery with ultra-high magnifications and manufacturing method thereof |
| CN101752545A (en) * | 2008-12-03 | 2010-06-23 | 北京有色金属研究总院 | Electrode of lithium battery, preparation method of electrode and lithium battery adopting electrode |
| CN101764219A (en) * | 2008-12-24 | 2010-06-30 | 中国科学院金属研究所 | Cathode materials for carbon nano-tube composite lithium ion battery and preparation method thereof |
| US20120045691A1 (en) * | 2004-06-02 | 2012-02-23 | Mystic Technology Partners | Carbon nanotube based electrode materials for high performance batteries |
| CN102544502A (en) * | 2010-12-09 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery |
-
2012
- 2012-07-17 CN CN201210248503.1A patent/CN103545525B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1207572A1 (en) * | 2000-11-15 | 2002-05-22 | Dr. Sugnaux Consulting | Mesoporous electrodes for electrochemical cells and their production method |
| US20120045691A1 (en) * | 2004-06-02 | 2012-02-23 | Mystic Technology Partners | Carbon nanotube based electrode materials for high performance batteries |
| CN101207193A (en) * | 2006-12-21 | 2008-06-25 | 比亚迪股份有限公司 | Method for preparation of electrode slurry |
| CN101567469A (en) * | 2008-07-08 | 2009-10-28 | 周雨方 | Power polymer lithium ion battery and fabricating process thereof |
| CN101335347A (en) * | 2008-08-01 | 2008-12-31 | 黄德欢 | Preparing method of highly conductive lithium iron phosphate anode material of lithium ionic cell |
| CN101752545A (en) * | 2008-12-03 | 2010-06-23 | 北京有色金属研究总院 | Electrode of lithium battery, preparation method of electrode and lithium battery adopting electrode |
| CN101764219A (en) * | 2008-12-24 | 2010-06-30 | 中国科学院金属研究所 | Cathode materials for carbon nano-tube composite lithium ion battery and preparation method thereof |
| CN101651236A (en) * | 2009-08-31 | 2010-02-17 | 杭州万马高能量电池有限公司 | Fast chargeable lithium iron phosphate polymer lithium ion battery with ultra-high magnifications and manufacturing method thereof |
| CN102544502A (en) * | 2010-12-09 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106463710A (en) * | 2014-04-25 | 2017-02-22 | 南达科他州评议委员会 | High capacity electrodes |
| CN105336922A (en) * | 2014-08-08 | 2016-02-17 | 苏州格瑞动力电源科技有限公司 | Preparation method and application for lithium ion battery negative electrode material based on photovoltaic silicon waste material |
| CN105336922B (en) * | 2014-08-08 | 2018-09-07 | 江苏载驰科技股份有限公司 | A kind of preparation method and application of the lithium ion battery negative material based on photovoltaic scrap silicon |
| CN104577117A (en) * | 2014-12-29 | 2015-04-29 | 山东精工电子科技有限公司 | Low-internal resistance lithium ion battery and preparation method thereof |
| CN104909434A (en) * | 2015-06-02 | 2015-09-16 | 吉林大学 | Manufacturing method of lithium iron phosphate three-dimensional electrode |
| CN105336942A (en) * | 2015-11-19 | 2016-02-17 | 上海空间电源研究所 | Fully-sealed Li-ion storage battery based on ternary cathode material and preparation method of fully-sealed Li-ion storage battery |
| CN107275598A (en) * | 2017-05-27 | 2017-10-20 | 广东烛光新能源科技有限公司 | A kind of lithium titanate anode material and preparation method thereof |
| CN107275598B (en) * | 2017-05-27 | 2020-02-14 | 广东烛光新能源科技有限公司 | Lithium titanate negative electrode material and preparation method thereof |
| CN108384237A (en) * | 2018-03-22 | 2018-08-10 | 苏州聚康新材料科技有限公司 | The preparation method of nickel based conductive nanocomposite |
| CN113366667B (en) * | 2019-01-30 | 2023-11-24 | Sk新能源株式会社 | Secondary battery and method for manufacturing same |
| CN113366667A (en) * | 2019-01-30 | 2021-09-07 | Sk新技术株式会社 | Secondary battery and method for manufacturing same |
| CN109980199B (en) * | 2019-03-20 | 2020-09-29 | 宁德新能源科技有限公司 | Negative active material, method for preparing same, and device using same |
| CN109980199A (en) * | 2019-03-20 | 2019-07-05 | 宁德新能源科技有限公司 | Negative electrode active material and preparation method thereof and the device for using the negative electrode active material |
| CN112786846A (en) * | 2019-11-08 | 2021-05-11 | 恒大新能源技术(深圳)有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN112786846B (en) * | 2019-11-08 | 2022-08-19 | 恒大新能源技术(深圳)有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN111292874A (en) * | 2020-03-23 | 2020-06-16 | 智能容电(北京)科技有限公司 | High-conductivity yield electrode material and preparation method thereof |
| CN111292874B (en) * | 2020-03-23 | 2022-10-14 | 智能容电(北京)科技有限公司 | High-conductivity yield electrode material and preparation method thereof |
| CN111370678A (en) * | 2020-05-27 | 2020-07-03 | 湖南雅城新材料有限公司 | Preparation method of modified lithium iron phosphate material for coated lithium battery |
| CN111900392A (en) * | 2020-06-22 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Positive plate and lithium ion battery containing same |
| CN112490408A (en) * | 2020-12-03 | 2021-03-12 | 珠海冠宇电池股份有限公司 | Positive plate and lithium ion battery comprising same |
| WO2023005988A1 (en) * | 2021-07-28 | 2023-02-02 | 比亚迪股份有限公司 | Positive electrode and battery |
| WO2023024625A1 (en) * | 2021-08-25 | 2023-03-02 | 贝特瑞新材料集团股份有限公司 | Negative electrode material and preparation method therefor, and lithium-ion battery |
| CN114883557A (en) * | 2022-03-07 | 2022-08-09 | 上海交通大学 | Preparation method of lithium iron phosphate composite positive electrode material with gold nanorods as conductive additive |
| WO2024021086A1 (en) * | 2022-07-29 | 2024-02-01 | 宁德时代新能源科技股份有限公司 | Negative electrode slurry, preparation method therefor, negative electrode sheet, battery cell, battery, and electric device |
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